US7820295B2 - Fluorine-doped tin oxide transparent conductive film glass and method of fabricating the same - Google Patents

Fluorine-doped tin oxide transparent conductive film glass and method of fabricating the same Download PDF

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US7820295B2
US7820295B2 US12/004,367 US436707A US7820295B2 US 7820295 B2 US7820295 B2 US 7820295B2 US 436707 A US436707 A US 436707A US 7820295 B2 US7820295 B2 US 7820295B2
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transparent conductive
conductive film
layer
glass
fto transparent
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US20090053511A1 (en
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Sang Hak Kim
Chang Yeol Kim
Doh Hyung Riu
Seung Hun Huh
Kwang Youn Cho
Chul Kyu Song
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Hyundai Motor Co
Korea Institute of Ceramic Engineering and Technology KICET
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Hyundai Motor Co
Korea Institute of Ceramic Engineering and Technology KICET
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Assigned to HYUNDAI MOTOR COMPANY, KOREA INSTITUTE OF CERAMIC ENG. & TECH. reassignment HYUNDAI MOTOR COMPANY ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: CHO, KWANG Y., HUH, SEUNG H., Kim, Chang Y., KIM, SANG H., RIU, DOH H., SONG, CHUL K.
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    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B17/00—Layered products essentially comprising sheet glass, or glass, slag, or like fibres
    • B32B17/06—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material
    • B32B17/10—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin
    • B32B17/10005—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin laminated safety glass or glazing
    • B32B17/10009—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin laminated safety glass or glazing characterized by the number, the constitution or treatment of glass sheets
    • B32B17/10036—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin laminated safety glass or glazing characterized by the number, the constitution or treatment of glass sheets comprising two outer glass sheets
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B17/00—Layered products essentially comprising sheet glass, or glass, slag, or like fibres
    • B32B17/06—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material
    • B32B17/10—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin
    • B32B17/10005—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin laminated safety glass or glazing
    • B32B17/10165—Functional features of the laminated safety glass or glazing
    • B32B17/10174—Coatings of a metallic or dielectric material on a constituent layer of glass or polymer
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B17/00—Layered products essentially comprising sheet glass, or glass, slag, or like fibres
    • B32B17/06—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material
    • B32B17/10—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin
    • B32B17/10005—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin laminated safety glass or glazing
    • B32B17/1055—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin laminated safety glass or glazing characterized by the resin layer, i.e. interlayer
    • B32B17/10761—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin laminated safety glass or glazing characterized by the resin layer, i.e. interlayer containing vinyl acetal
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
    • C03C17/22—Surface treatment of glass, not in the form of fibres or filaments, by coating with other inorganic material
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
    • C03C17/34—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions
    • C03C17/36—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions at least one coating being a metal
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
    • C03C17/34—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions
    • C03C17/36—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions at least one coating being a metal
    • C03C17/3602—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions at least one coating being a metal the metal being present as a layer
    • C03C17/3668—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions at least one coating being a metal the metal being present as a layer the multilayer coating having electrical properties
    • C03C17/3673—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions at least one coating being a metal the metal being present as a layer the multilayer coating having electrical properties specially adapted for use in heating devices for rear window of vehicles
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C2217/00—Coatings on glass
    • C03C2217/70—Properties of coatings
    • C03C2217/77—Coatings having a rough surface
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C2217/00—Coatings on glass
    • C03C2217/90—Other aspects of coatings
    • C03C2217/94—Transparent conductive oxide layers [TCO] being part of a multilayer coating
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/26—Web or sheet containing structurally defined element or component, the element or component having a specified physical dimension
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/31504—Composite [nonstructural laminate]
    • Y10T428/31678—Of metal
    • Y10T428/31692—Next to addition polymer from unsaturated monomers
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/31504—Composite [nonstructural laminate]
    • Y10T428/31844—Of natural gum, rosin, natural oil or lac
    • Y10T428/31848—Next to cellulosic
    • Y10T428/31851—Natural oil

Definitions

  • the present invention relates to a fluorine-doped tin oxide (FTO) transparent conductive film glass having low resistance and high transmittance and a method of fabricating the same. More particularly, the present invention relates to an FTO transparent conductive film glass used for defogging purposes comprising a glass layer, a dielectric barrier layer, a functional layer, a metal electrode layer, a plastic intermediate layer, and a glass layer, stacked in the order, in which the functional layer comprises an FTO transparent conductive film having low resistance and high transmittance, and a method of fabricating the same.
  • FTO transparent conductive film glass used for defogging purposes comprising a glass layer, a dielectric barrier layer, a functional layer, a metal electrode layer, a plastic intermediate layer, and a glass layer, stacked in the order, in which the functional layer comprises an FTO transparent conductive film having low resistance and high transmittance, and a method of fabricating the same.
  • electrode materials having high transmittance of visible light have been used to prepare various electrodes of heating resistors for anti-fogging or anti-icing purposes adapted in window glasses of vehicles, airplanes, buildings, etc., or electrodes of display devices such as liquid crystal display devices, plasma display panels, electroluminescence display devices, etc.
  • Such transparent conductive materials include antimony-doped tin oxide (ATO), indium tin oxide (ITO), and the like, in which the ITO having a low specific resistance has been widely used.
  • ATO antimony-doped tin oxide
  • ITO indium tin oxide
  • the ITO transparent conductive film glass is formed by applying heat at about 500° C.
  • electrical properties of the ITO are affected, and its heat resistance, chemical resistance and abrasion resistance, for example, are reduced.
  • FTO fluorine-doped tin oxide
  • U.S. Pat. No. 2,566,346 discloses a method of applying a fluoride solution capable of being ionized with a tin compound to a glass substrate heated at about 400° C.
  • U.S. Pat. No. 3,107,177 discloses a method of applying a solution comprising an organic tin compound, 4% hydrochloric solution and an ionizable fluoride to a heated substrate so as to fabricate a transparent, electrically conductive tin oxide thin film having a haze of 1% or less.
  • U.S. Pat. No. 3,677,814 discloses a method in which an organic tin compound having a tin-fluorine bond is formed by pyrolysis.
  • the first and second methods have drawbacks in that vacuum should be provided, and complicated and expensive equipments for providing gases and precursors are necessary.
  • U.S. Pat. No. 3,959,565 discloses a method of intermittent spraying a non-aqueous solution in an oxidizing atmosphere to coat a tin oxide.
  • U.S. Pat. Nos. 4,146,657 and 4,500,567 disclose methods of manufacturing an electrically conductive tin oxide thin film by a process of utilizing gaseous chemical compounds.
  • the method of intermittent spraying has a drawback in that it requires a lot of processing time, and the methods of utilizing gaseous chemical compounds have a drawback in that the cost of raw material is high. These methods thus are not suitable for preparation of such electrically conductive tin oxide thin film for defogging purposes.
  • a dielectric barrier layer is disposed between the FTO transparent conductive film and the glass substrate to achieve high transmittance of the windshield.
  • the dielectric barrier layer is introduced to prevent a decrease in transmittance due to change of the color of the windshield which is caused by diffusion of Na ions of the glass layer into the FTO transparent conductive film.
  • Such technologies related to the dielectric barrier layer disposed between the FTO transparent conductive film and the glass substrate are disclosed in U.S. Pat. Nos. 3,378,396, 4,187,336 and 5,028,566.
  • the above-described prior art technologies have some drawbacks in that it is difficult to continuously form the transparent conductive film on the dielectric barrier layer and thus the processing speed is very low. Accordingly, the prior art technologies are not suitable for preparing the transparent conductive film as the windshield for defogging purposes.
  • One object of the present invention is to provide a fluorine-doped tin oxide (FTO) transparent conductive film glass having low resistance and high transmittance and a method of fabricating the same, in which the FTO transparent conductive film glass includes an FTO transparent conductive film having excellent heat resistance, chemical resistance and abrasion resistance, low resistance and high transmittance.
  • FTO transparent conductive film glass which generates heat when electricity is applied thereto, can be effectively used as a windshield for defogging purposes.
  • Another object of the present invention is to provide an FTO transparent conductive film glass including an FTO transparent conductive film having a specific molar ratio of fluorine (F) to tin (Sn) to provide low resistance and high transmittance and mainly including a (301) crystal plane.
  • Still another objects of the present invention is to provide an FTO transparent conductive film glass including an FTO transparent conductive film formed by a spray coating method which can readily control the specific molar ratio and the crystal plane.
  • a fluorine-doped tin oxide (FTO) transparent conductive film glass comprising a glass layer, a dielectric barrier layer, a functional layer, a metal electrode layer, a plastic intermediate layer, and a glass layer, stacked in this sequential order, in which the functional layer comprises an FTO transparent conductive film having a molar ratio of F to Sn in the range of 0.5 to 2 and a ratio between a (200) crystal plane and a (301) crystal plane in the range of 1:4 to 1:1 (texture coefficient).
  • FTO fluorine-doped tin oxide
  • the present invention provides a method of fabricating a fluorine-doped tin oxide (FTO) transparent conductive film glass, the method comprising: forming a precursor solution by dissolving a tin oxide precursor and a fluorine precursor in deionized water; and spray-coating the precursor solution on the top surface of the dielectric barrier layer in the temperature range of 400 to 550° C. under air atmosphere, thus forming an FTO transparent conductive film having a molar ratio of F to Sn in the range of 0.5 to 2 and a ratio between a (200) crystal plane and a (301) crystal plane in the range of 1:4 to 1:1 (texture coefficient) as the functional layer.
  • FTO fluorine-doped tin oxide
  • FIG. 1 depicts a process in which a film spray-coated with an FTO coating solution is crystallized
  • FIG. 2 is a graph depicting the results of X-ray crystal structure (XRD analysis, scan speed: 5°/min) of a film spray-coated with an FTO coating solution in Example 2;
  • FIG. 3 is a graph depicting the results of X-ray crystal structure (XRD analysis, scan speed: 5°/min) of a film spray-coated with an FTO coating solution containing an alkyl group in Example 2;
  • FIG. 4 is a field emission-scanning electron microscope (FE-SEM) photography showing microstructures of a film spray-coated with an FTO coating solution;
  • FE-SEM field emission-scanning electron microscope
  • FIG. 5 is an FE-SEM photograph showing microstructures of a film spray-coated with an FTO coating solution containing an alkyl group
  • FIG. 6 is a graph depicting optical transmittances of (a) an FTO transparent conductive film glass formed using deionized water as a solvent, (b) an FTO transparent conductive film glass formed using a solvent containing an alkyl group, and (c) an FTO transparent conductive film formed using a solvent containing an alkyl group;
  • FIG. 7 is a schematic diagram depicting the configuration of an FTO transparent conductive film glass for defogging purposes having low resistance and high transmittance, in which reference numeral 1 denotes an oxide barrier layer, 2 denotes a transparent conductive film, 3 denotes an electrode, 4 denotes a glass substrate, and 5 denotes a polymer film;
  • FIG. 8 is a graph depicting heating characteristics according to applied voltages in Example 2 (heating temperatures about 300 seconds after applying voltages).
  • FIG. 9 is a graph depicting heating temperatures according to time lapse after applying a constant voltage of 8 V in Example 2.
  • the present invention provides an FTO transparent conductive film glass for defogging purposes, which comprises a glass layer, a dielectric barrier layer, a functional layer, a metal electrode layer, a plastic intermediate layer, and a glass layer, wherein the functional layer is formed by spray-coating a precursor solution, which is prepared by dissolving a tin oxide precursor and a fluorine precursor in deionized water, on the top surface of the dielectric barrier layer in the temperature range of 400 to 550° C. under air or oxygen atmosphere.
  • a spray coating method has advantages, as discussed above, in that the manufacturing cost is lower and the manufacturing process is simpler compared with the conventional sputtering and chemical vapor deposition (CVD) methods.
  • any spray coating methods that are known in the art can be used and it is not limited to a any particular method.
  • a spray coating method using an air nozzle or ultrasonic spray nozzle may be employed.
  • the spray solution for spray-coating the functional layer of the FTO transparent conductive film glass for defogging purposes is characterized in that it does not contain any alcohol compound. Accordingly, the spray solution of the present invention has an advantage that controls the crystal plane to be softened and thus it is possible to form a transparent conductive film having less haze, compared with the conventional spray coating method, in which an alcohol compound is used and a thin film is formed with a rough surface to cause haze seriously.
  • the tin oxide precursor may be any one of those commonly used in the art and is not limited to any particular one.
  • the tin oxide precursor may be formed of any one selected from the group consisting of SnCl 4 .5H 2 O, SnCl 2 , and SnCl 2 .2H 2 O.
  • the fluorine precursor may be NH 4 F having no alkyl group.
  • the tin oxide precursor and the fluorine precursor used in the present invention are characterized in that they do not have an alkyl group. The reason for this is that the raw material having the alkyl group is expensive, and that the crystal growth surface in the direction of 200 is mainly grown to roughen the surface of the thin film, thus increasing the haze value remarkably.
  • the spray solution of the present invention uses deionized water solely as a solvent.
  • the deionized water inhibits the crystal growth of the FTO transparent conductive film so that surface microstructures are not excessively grown but smoothly grown to prevent light diffusion occurring on the surface, thus reducing the haze caused from the functional layer comprising the FTO transparent conductive film.
  • the fluorine content of the FTO transparent conductive film in accordance with the present invention is a significant factor affecting the conductivity and transmittance of the FTO transparent conductive film glass. Accordingly, the molar ratio of fluorine (F) to tin (Sn) is preferably in the range of 0.5 to 2.
  • the spray solution uses deionized water as a solvent, and the tin oxide material and NH 4 F are mixed in the molar ratio range of F to Sn. At this time, if the doping amount is too large, an extremely large amount of free electrons is generated in the tin oxide film and diffused to act as resistances against each other, thus reducing the electrical conductivity.
  • the number of the free electrons is increased to reduce the transmittance.
  • the doping amount is too small, an increase in the electrical conductivity is insignificant, and the crystal plane is randomly oriented.
  • the transmittance is high; however, the electrical specific resistance becomes high. Accordingly, it is preferable that the above range be maintained.
  • the spray solution is spray-coated on the top surface of the dielectric barrier layer in the temperature range of 400 to 550° C. under air or oxygen atmosphere. If the spray coating temperature exceeds 550° C., it is higher than the softening point of the glass substrate, and thus the glass substrate may be deformed. Whereas, if the spray coating temperature is below 400° C., the tin oxide is not crystallized, and thus the conductivity and transmittance of the transparent conductive film are significantly reduced. Accordingly, it is preferable that the above temperature range be maintained. Moreover, if not the air or oxygen atmosphere condition, the tin oxide is reduced to form metal tin, and thus the transmittance is significantly reduced. Accordingly, it is preferable that the above condition be maintained.
  • the thus formed FTO transparent conductive film is characterized in that the molar ratio of F to Sn is in the range of 0.5 to 2 and the ratio between the (200) crystal plane and the (301) crystal plane is in the range of 1:1 to 1:4.
  • FIG. 1 depicts a process in which a film spray-coated with an FTO coating solution is crystallized.
  • FIG. 3 in the conventional FTO transparent conductive film, triangular microstructures mainly having the (200) crystal plane are generally observed; however, it can be seen that the crystals in accordance with the present invention include the (301) crystal plane and the (200) crystal plane formed in the middle thereof.
  • such crystal microstructures of the present invention in which small crystals having the (200) crystal plane are present between large crystals having the (301) crystal plane, reduce the surface roughness to prevent the light diffusion occurring on the surface and reduce the haze, thus increasing the transparency of the thin film.
  • the thickness of the FTO transparent conductive film exceeds 1.3 ⁇ m, the visible light transmittance is significantly reduced, whereas, if it is below 0.1 ⁇ m, the electrical resistance is increased. Accordingly, it is preferable that the thickness of the FTO transparent conductive film be maintained in the range of 0.1 to 1.3 ⁇ m.
  • the present invention provides an FTO transparent conductive film glass for defogging purposes comprising a glass layer, a dielectric barrier layer, a functional layer, a metal electrode layer, a plastic intermediate layer, and a glass layer, in which the dielectric barrier layer is formed of SiO 2 or a mixture of SiO 2 and an oxide of a transition metal selected from the group consisting of Ti, Zr and Al in the temperature range of 200 to 500° C.
  • the dielectric barrier layer is introduced to prevent a decrease in transmittance caused by discoloration due to Na ions of the glass layer being diffused into the FTO transparent conductive film.
  • the dielectric barrier layer is formed with a thickness of 5 to 200 nm in consideration of coating process conditions and optical characteristics such as the visible light transmittance and reflection.
  • the compound including a Si oxide introduced into the dielectric barrier layer may be any one of those commonly used in the art and is not limited to any particular one.
  • the compound may be any one selected from the group consisting of tetraethylorthosilicate (TEOS) and titanium isopropoxide (TIP).
  • TEOS tetraethylorthosilicate
  • TIP titanium isopropoxide
  • the thus formed dielectric barrier layer may include a silica or mixed layer of silica and titanium oxide.
  • the dielectric barrier layer is formed in the temperature range of 200 to 500° C. If the temperature exceeds 500° C., it approaches the softening point of glass, and thus the glass may be deformed, whereas, if the temperature is below 200° C., impurities such as carbon may remain in the oxide film. Accordingly, it is preferable that the above temperature range be maintained.
  • the metal electrode layer may be any one of those commonly used in the art and is not limited to any particular one.
  • the metal electrode layer may be formed by coating silver paste for high temperature on the substrate, on which the glass layer, the dielectric barrier layer and the functional layer are stacked, by a screen printing method and heat treating the resulting substrate at 500° C. for 10 minutes.
  • the thus formed substrate, on which the glass layer, the dielectric barrier layer, the functional layer and the metal electrode layer are stacked is bonded to another glass layer by applying pressure at 90° C. using a plastic intermediate layer.
  • the plastic intermediate layer may be any one of those commonly used in the art and is not limited to any particular one.
  • the plastic intermediate layer may be any one selected from the group consisting of polyvinyl butyral (PVB), ethylene-vinyl acetate copolymer (EVA) and urethane intermediate layers.
  • PVB polyvinyl butyral
  • EVA ethylene-vinyl acetate copolymer
  • urethane intermediate layers urethane intermediate layers.
  • the PVB intermediate layer has excellent penetration resistance and is chemically and optically stable for a long period of time, it is generally used as an assembly of a laminated glass for a vehicle. Accordingly, in order to provide excellent penetration resistance to the FTO transparent conductive film glass, it is more preferable that the PVB intermediate layer be used as the plastic intermediate layer.
  • the glass layer used in the present invention may be any one of those commonly used in the art and is not limited to any particular one.
  • the glass layer may be any one selected from the group consisting of a borosilicate glass, a soda-lime glass for use as an ordinary window and a clear soda-lime glass for a vehicle.
  • the dielectric barrier layer for preventing Na ions from being diffused is not required.
  • the present invention provides the FTO transparent conductive film glass for defogging purposes including the FTO transparent conductive film having excellent heat resistance, chemical resistance and abrasion resistance, low resistance and high transmittance formed using a simpler and cheaper spray coating method.
  • the FTO transparent conductive film glasses according to the present invention have the specific resistance in the range of 3 ⁇ 10 ⁇ 4 to 12 ⁇ 10 ⁇ 4 ⁇ cm, the sheet resistance in the range of 3 to 12 ⁇ /sq, the transmittance in the range of 70 to 85%, and the temperature rise rate at 8 V in the range of 3 to 5° C./min.
  • the FTO transparent conductive film glasses which generates heat when electricity is applied thereto, may be effectively used as a windshield, an ordinary window glass, and a borosilicate glass for defogging purposes.
  • the FTO transparent conductive film was introduced as the functional layer, and the effect of the molar ratio of F to Sn was studied by changing the molar ratio of F to Sn 0.5 in Preparation Example 1 and 1.76 in Preparation Example 2.
  • a soda-lime glass was used as the glass layer, and the dielectric barrier layer was formed at 500° C. by a sol-gel processing method, thus forming a silicon oxide layer with a thickness of 0.05 ⁇ m.
  • the FTO transparent conductive film was formed by a spray coating method, in which the spray solution was formed by mixing SnCl 4 .5H 2 O used as a Sn precursor and NH 4 F used as an F precursor with 100 g of a water solvent so that the molar ratio of F to Sn may be 0.5 in Preparation Example 1 and 1.76 in Preparation Example 2.
  • the thus formed spray solution was coated on the top surface of a substrate comprising a glass layer and a dielectric barrier layer in a thickness of 1 ⁇ m at 530° C. by ultrasonic spray pyrolysis. The process in which such a film spray-coated with the FTO coating solution was crystallized was depicted in FIG. 1 .
  • the effect of the thickness of the dielectric barrier layer was studied by changing the thickness of the dielectric barrier layer to 0.1 ⁇ m in this Preparation Example.
  • Other conditions than the thickness of the dielectric barrier layer were the same as Preparation Example 2, in which the thickness of the dielectric barrier layer was 0.05 ⁇ m.
  • an FTO transparent conductive film glass for defogging purposes comprising a glass layer, a dielectric barrier layer, a functional layer, a metal electrode layer, a plastic intermediate layer, and a glass layer, stacked in this sequential order, in which the metal electrode layer was formed by coating silver (Ag) paste by a screen printing method on the unit film comprising the glass layer, the dielectric barrier layer and the FTO transparent conductive film, prepared in Preparation Examples 1 (Example 1) and 2 (Example 2), respectively, and by heating at a temperature of about 500° C. for 10 minutes.
  • the thickness of the metal electrode layers was about 1 ⁇ m.
  • a PVB film was introduced as a plastic intermediate layer to compress each of the thus prepared unit films comprising the glass layer, the dielectric barrier layer, the FTO transparent conductive film and the metal electrode layer with a separate glass layer.
  • the FTO transparent conductive film glasses comprising the PVB film were formed by heating and compressing at about 90° C.
  • an FTO transparent conductive film glass for defogging purposes comprising a glass layer, a dielectric barrier layer, a functional layer, a metal electrode layer, a plastic intermediate layer, and a glass layer, stacked in this sequential order, in which the functional layer was formed by controlling the solvent, the coating atmosphere, and the starting material under the ultrasonic spray coating process so that the ratio between the (200) crystal plane and the (301) crystal plane might be in the range of 1:1 in this Example, and compared with Example 2.
  • the methods of introducing the metal electrode layer and compressing the unit film comprising the glass layer, the dielectric barrier layer, the FTO transparent conductive film and the metal electrode layer with a separate glass layer were the same as Example 2.
  • an FTO transparent conductive film glass for defogging purposes comprising a glass layer, a dielectric barrier layer, a functional layer, a metal electrode layer, a plastic intermediate layer, and a glass layer, stacked in sequential order, in which the metal electrode layer was formed by coating silver (Ag) paste by a screen printing method on the unit film comprising the glass layer, the dielectric barrier layer and the FTO transparent conductive film, prepared in Comparative Preparation Examples 1 to 4, respectively, in Comparative Examples 1 to 4, and by heating at a temperature of about 500° C. for 10 minutes.
  • the thickness of the metal electrode layer was about 1 ⁇ m.
  • a PVB film was introduced as a plastic intermediate layer to compress each of the thus prepared unit films comprising the glass layer, the dielectric barrier layer, the FTO transparent conductive film and the metal electrode layer with a separate glass layer.
  • the FTO transparent conductive film glasses comprising the PVB film were formed by heating and compressing at about 90° C.
  • an FTO transparent conductive film glass for defogging purposes comprising a glass layer, a dielectric barrier layer, a functional layer, a metal electrode layer, a plastic intermediate layer, and a glass layer, stacked in sequential order, in which the functional layer was formed by controlling the solvent, the coating atmosphere, and the starting material under the ultrasonic spray coating process so that the ratio between the (200) crystal plane and the (301) crystal plane might be in the range of 1:0.1 in Comparative Example 5, and in the range of 1:0.5 in Comparative Example 6.
  • the methods of introducing the metal electrode layer and compressing the unit film comprising the glass layer, the dielectric barrier layer, the FTO transparent conductive film and the metal electrode layer with a separate glass layer were the same as Example 2.
  • Example 4 ′′ ′′ 300 ′′ ′′ ′′ ′′ Deionized ′′ ′′ ′′ water P.
  • Example 5 ′′ 0.1 500 ′′ ′′ ′′ ′′ Deionized ′′ ′′ ′′ water P.
  • Example 6 TiO 2 ′′ ′′ ′′ ′′ ′′ ′′ Deionized ′′ ′′ ′′ water P.
  • Example 7 ZrO 2 ′′ ′′ ′′ ′′ ′′ Deionized ′′ ′′ ′′ water Comparative SiO 2 0.05 ′′ 0.1 ′′ ′′ ′′ Deionized ′′ ′′ ′′ Preparation water (C.P.)
  • Example 1 C.P.
  • Example 2 ′′ ′′ ′′ 0.3 ′′ ′′ ′′ Deionized ′′ ′′ ′′ water C.P.
  • Example 3 ′′ ′′ ′′ 2.3 ′′ ′′ ′′ Deionized ′′ ′′ ′′ water C.P.
  • Example 4 ′′ ′′ ′′ 2.5 ′′ ′′ ′′ Deionized ′′ ′′ ′′ water C.P.
  • Example 5 ′′ ′′ 100 1.76 ′′ ′′ ′′ Deionized ′′ ′′ ′′ water C.P.
  • Example 6 ′′ 1 500 ′′ ′′ ′′ ′′ Deionized ′′ ′′ ′′ water C.P.
  • Example 7 2 ′′ ′′ ′′ ′′ ′′ Deionized ′′ ′′ ′′ water C.P.
  • Example 8 — 0.05 ′′ ′′ ′′ ′′ ′′ Deionized ′′ ′′ ′′ water C.P.
  • Example 10 ′′ ′′ ′′ ′′ ′′ ′′ ′′ Deionized Spray coating 200 1 water C.P.
  • Example 12 ′′ ′′ ′′ ′′ ′′ ′′ Deionized ′′ 530 1.5 water C.P.
  • Example 14 ′′ ′′ ′′ ′′ 1:0.1 DMTC ′′ Deionized ′′ ′′ 1 MBTC water TMT C.P.
  • Example 15 ′′ ′′ ′′ ′′ ′′ ′′ SnCl 4 •5H 2 O Acetyl- Deionized ′′ ′′ ′′ fluoride water C.P.
  • Example 16 ′′ ′′ ′′ ′′ ′′ NH 4 F Ethanol + ′′ ′′ ′′ Deionized water
  • Example 1 ′′ ′′ ′′ 0.5 1:4 ′′ ′′ Deionized ′′ ′′ ′′ water
  • Example 3 ′′ ′′ ′′ 1:1 ′′ ′′ Deionized ′′ ′′ ′′ water Comparative ′′ ′′ ′′ 0.1 1:4 ′′ ′′ Deionized ′′ ′′ ′′ (C)
  • Example 1 water C.
  • Example 2 ′′ ′′ ′′ 0.3 ′′ ′′ ′′ Deionized ′′ ′′ ′′ water C.
  • Example 3 ′′ ′′ ′′ 2.3 ′′ ′′ ′′ Deionized ′′ ′′ ′′ water C.
  • Example 4 ′′ ′′ ′′ 2.5 ′′ ′′ ′′ Deionized ′′ ′′ ′′ water C.
  • Example 5 ′′ ′′ ′′ 1.76 1:0.1 ′′ ′′ Deionized ′′ ′′ ′′ water C.
  • Example 6 ′′ ′′ ′′ ′′ 1:0.5 ′′ ′′ Deionized ′′ ′′ ′′ water
  • the specific resistance is directed to the evaluation of electrical characteristics of the transparent conductive films.
  • the specific resistance values were measured by a 4-point probe method and by multiplying the thickness of the thin film thereto.
  • the results measured using the Hall coefficient measurement HMS 3000 are shown in Table 2.
  • the sheet resistance is a property directly related to the final moisture removal characteristics of the transparent conductive film. The lower the resistance is, the higher the heat generation amount is at low voltage. Accordingly, it is possible to readily remove the moisture at low voltage.
  • the method of measuring the sheet resistance and the measurer are the same as the method of measuring specific electrical resistance.
  • the sheet resistance denotes an electrical resistance value in which the thickness of the thin film is not considered. The results of the sheet resistance are shown in Table 2.
  • the transmittance in visible light region is important in the transparent conductive film. If the thickness of the transparent conductive film is increased, the transmittance tends to be reduced. Moreover, the transmittance may be reduced by the orientation of crystals in the thin film, the size of crystal particles, and the roughness of the surface.
  • the transmittances were measured in the wavelength of 200 to 2500 nm using a transmittance measurer (UV/VIS/NIR photospectrometer, JASCO, V570), and the results are shown in Table 2.
  • the XRD diffraction characteristics were measured to evaluate the crystallinity of the thin film and the orientation of the crystals in the thin film.
  • the results measured by XRD are shown as texture coefficient of the (200) and (301) crystal planes in FIGS. 2 and 3 .
  • the heating characteristics can be evaluated by measuring the increase in temperature by heat generated when applying a constant voltage to the glass.
  • the temperature changes were measured using a potentiostat and a K-type thermometer when applying a constant voltage, and the measured results are shown in FIGS. 8 and 9 .
  • Example 6 ′′ 7 7 60 C.P.
  • Example 8 100 100 70 C.P.
  • Example 9 ′′ 5 170 80 Sol-gel coating method with thickness 0.3 ⁇ m C.P.
  • Example 10 ′′ — — — Film not formed C.P.
  • Example 11 ′′ — — Film not formed C.P.
  • Example 12 ′′ 2.3 1.6 40 C.P.
  • Example 14 ′′ 3 3 50 C.P.
  • Example 15 3 3 3 50 C.P.
  • Example 16 ′′ 3 3 50 Example 1 FTO transparent 12 12 80 conductive film glass
  • the dielectric barrier layers formed in the temperature range of 200 to 500° C. could prevent Na ions from being diffused sufficiently and had low specific resistance and high transmittance of visible light.
  • the FTO transparent conductive film prepared by the sol-gel coating method in accordance with Comparative Preparation Example 9 had a drawback in that the coating process should be carried out at least two times to form a thickness of more than 0.3 ⁇ m. It could be seen that the thus prepared FTO transparent conductive film had high sheet resistance. Moreover, if the temperature in preparing the FTO transparent conductive film was less than 400° C. in Comparative Preparation Examples 10 and 11, the tin oxide was not crystallized, and thus the thin film was not formed. Accordingly, it could be understood that the temperature range of 400 to 550° C. was most appropriate in consideration of the deformation of the glass substrate. In the case where the thickness of the FTO transparent conductive films prepared in accordance with Comparative Preparation Examples 11 and 12 was large, the sheet resistance could be reduced; however, the visible light transmittance was reduced.
  • an FTO transparent conductive film glass having a sheet resistance of 4.5 ⁇ /sq was prepared for the purpose of defogging the windshield, and the heating temperatures measured according to applied voltages were shown in the graph.
  • the heating temperature was increased linearly according as the voltage was increased and, especially, when a voltage of 8 V was applied, the heating temperature was increased from about 16° C. up to 71° C.
  • the heating temperature was increased about 40° C. from 20° C. to 60° C. about 9 minutes after applying a constant voltage of 8 V.
  • Such heating characteristics mean that the temperature can be increased up to the melting point of water even from the outer environment of ⁇ 40° C. within about 9 minutes after applying a voltage of 8 V. Accordingly, the FTO transparent conductive film glass in accordance with the present invention can be effectively used as a windshield for defogging purposes.
  • the present invention provides an FTO transparent conductive film glass comprising a glass layer, a dielectric barrier layer, a functional layer, a metal electrode layer, a plastic intermediate layer, and a glass layer, stacked in sequential order, in which the functional layer comprises an FTO transparent conductive film formed by a spray coating method. Accordingly, the present invention has advantageous effects in that the manufacturing cost is low, the manufacturing process is simple, and the FTO transparent conductive film glass has excellent heat resistance, chemical resistance and abrasion resistance, low resistance and high transmittance. Moreover, such an FTO transparent conductive film glass, which generates heat when electricity is applied thereto, may be effectively used as a windshield, an ordinary window glass, and a borosilicate glass for defogging purposes.

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JP7143919B1 (ja) 2021-05-07 2022-09-29 Ａｇｃ株式会社 透明導電膜付きガラス基板及びその製造方法
KR20240027535A (ko) 2022-08-23 2024-03-04 인디언 오일 코퍼레이션 리미티드 태양광 물 분해를 위한 양면 광활성 반도체 재료를 위한 재사용 가능한 금속 기판
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US20090053511A1 (en) 2009-02-26
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